Manufacture of diacidyl and higher acidylated compounds from amino-azo bases.



' mam-Bren ""JNETED PATENT QFFEQE,

earns-Anna, or statement, on

RMAN'Y, ASSIGNOR- TO THE 'EIRI VI OF KALLE W'MPANY, AKTIENG-ESEBLSGHAFT. F BI'EBRICH; GERMANY. I

" lmnnnoiwnn or nmornnn nits: Hie-nan ecxnynernn oomroonnsrnoz AMINO- q Ms BASES.

Q In the Eerie/tie lh all wltorroit mag conceanr' doctor of philosophy end, zchem'istgj l bl of the Grand; Duke of fiiebrich-bn-the llhine Hesse; residing at Germany; have mtionr v I tier Deutschen C e iscfzien GeseZZsc/Tzdft -'Vol. 17, pages 4'63 and 4.70, ere described itheacetyl-emidoezo-benzene '(meltingpoinftfI lP Centigrade) "and ecetyl eniido ezotoluene' 185 centigrede)', both being; I bteined by heetingthe corresponding bas sit acetic very reedy conversion into acidyl end especially d'i-ecjt' enhyclricl. The amino-azo-benzene derive tive has been obtained by 'Be'rju, see Beriohteyvol lf page 1400, (melting point 143 centigrade and. indirectly also by (ineltingegoint' froin 1441to 146 centigratie').

thesecases only'the mono-alcetyl derivatives were obtained. r v i I heye found, thaiternino-ezo-henzene, its

derivatives homologuesisnd analogues, n-

I 'the following generalforniule 1 where R and RY; arethe-aromatic nuclei of the ecirlj lemido-ezo compounds. If the amino-e20 derivatives used .possessvseveral amino A possible. In order to obtain th sresult it necessary to work with sufficiently lerg e excessof the ecetylating vagent and to employ a high temperature-for e sufiioiently long periodi The employment of {the acetylating" agents usually employeil in lieu of acetic anhydricl presents no advantage in practice. For instance, as also Berju, boiling with glacial acetic only mono-aoetyl-amido-azo-benzene acid gives and likewise 1nono-acetyl-ezo-toluene can be ob tained in the same manner and moreover the yield is not good and dark colored byprocliicts are formed, The conditions are i I i Specification of matters Patent. e neation n ea September 9, Isle. Serial No. 719,421.

Dieoid zl anolJHighe'r 1 sodium precipitateclwith I hatter removal oft'he'excess of anhydrid and (m lting point f the amino'nzo telnene derive tive 'hrie'f'niention 'is made "the SpgCl'fiCHr" "tion of German-Patent No. 88,013; In all,

groups, evenv a" higher acetylation is stated by ?atented 0etn 28, 1913;

einpleyeti; I

".llhe"following are'examples ofhow this invent ionmay becarried out in practice, but the invention is not limited thereto.

similar when for instance acetyl chlorid is Example 1: 50 kilograms of amino-ozotoluene-are hoile'din a refluxcondenser With ah0ut l50 kilograms "of acetic anhydrid with the addition of from 10 to 20 kilogrzims of ecetete'n-ntil (usually after from 4 to 10- hciirs) a sample of theinelton cooling nolonger deposits crystals. The melt is then water either directly, or

acetic acid, enil' the raw product" which soon solidifies is recrystallized out of alcohol for instance. ."In this Way nearly e practically theoretical yield of the'di-a'cetyl compound formula \He on crn is obtained; Separation from the small finiounts of mono-ecetyl derivative which are'sometimes present is scarcely 11C8SSiLI' Di-ecet l-amido-azo-toluene forms long rel dish-y 0W needles "having a melting point r of'65? centigrade, or thick crystals of a fine red color similar to potassium dich'roinate,

which ,ciystelshave a melting'p'oint'of 75 c cen-tigr e. i In both crystalline forms it readily dissolves in many solvents; 'While i themono-ecetyl (lerivetite is diflicultly .sol-

uble, or evenonl; soluble in traces. It is therefore possible to re ove even small amounts of the mono-weevil com blind. The statement of Schultz (Bericlnte1%;page 1:70) that acetyl einideem-toluene (melting point 185 .Cei1tig-rede) is readily soluble in alcohol is erromeous.

Example II 50 kilogrziins' of amino-azobenzene are-boilecl-in a refiu'xcondenser with from about 200 to 25Okil9gra1ns of acetic anhydrid, preferably with the addition of 4 20 kilograms of sodium acetate, until it sample of the melt on cooling no longer precipitotes crystals. is the same as in Example l. The di-acetyiation of the emino-azo-benzene takes place somewhat more diflicultly than does the liacetylation of the corresponding toluene In other respects the process toluene derivative.

the foregoin compounds 0' the benzene, or naphthalene compo Ql, and consequently in the use or so small an amount of acetic anhydi-id as mentioned in Example too mi'ich niono-acetyl derivative is produced. Di-acetyl-amidoazo-benzene 1T N/(E CH c--cii,

- series can be used, f. 'i. the substitution prod-- octe oi.- hoinologues thereof.

new compounds are in therapeutics. Compared azo compounds the: it

guished by the tact {lint th 7 c not poison one in d not irritant. They have over the ii the amino are distin- 'iiiflicultly solubie mono-acidyl derivatives the advantage of greater solubilit are more economical in use an intense action.

I claim;

1. The process of producing from amino azo bases acidyl compounds containing at least one acidyl group more while they have amore in heating. the suit bases with an excess of an acidylatmg agent over the amount theoretically required.

2. The process of producing from amino- '5 two bases acetyl compounds containing at jam-toluene, insoluble in water readil soluble in the usual organic solvents, an cryitallizing' therefrom either in 'long reddish-- yellow needles of a melting least one acetyl group more than the number of amino groups, w ich process consists in heating the said bases with an. excess of an acetylating' agent over the amount theoretically required.

3. The process of producing from amino .azo bases acetyl compounds containing at least one acetyl group more than, the numher of amino grou s, which'process consists bases with an excess of in heating the sai the amount theoretiacctic anhydrid over cally required.

{Lids new products the acidyl compounds than the number of amino grou s, which process consists l lete separation.

I tives of amino-azo bases of t I of the following general formula generally soluble inorganic solvents.

suitable for use l 4 rivatives of amino-azo bases 0 series of the following general formula and crystallize from amino-am bases containing at least one acidyl group more than the number of amino groups and obtainable by heating amino-azo bases with an excess of an acidv ating agent over the amount theoretic required.

from amino-zizo bases containing at least 6 one acetyl group more than the number of. the amino cups and obtainable by heating amino-azo uses with an excess of an acct ating agent over the amount theoretically required.

6. As new products diacidyl derivatives of mono-amino-azo bases, obtainable by heati amino-azo bases with an excess of an acidv ating agent over the amount t-heoretica 1y required, insoluble in water and generally soluble in organic solvents.

7. As new products diacetyl derivatives of niono-amiiio-azo bases, obtainable by heating ammo-azo bases with an excess of an acetylating agent over the amount theore'tically required, insoluble in water and 8. As new products diacidvl-amino dethe benzene aciilyl 9. As new products diacetKl-amino derivee benzene seriel s-s mmit acetyl where R and R are aryl nuclei, insoluble in water, generall soluble in organic solvents,

le therefrom. 10. As a new product the diacetyl-amino- Y HEINRICH REINHARPT Witnesses:

Auous'r Born, HERMAN PLISOHERE.

5. As new products the acetyl compounds where R and R are aryl nuclei, insoluble in 5 water, generally soluble in organic solvents, and crystallizable therefrom. 

